Method for solution hardening of a cold deformed workpiece of a passive alloy, and a member solution hardened by the method

ABSTRACT

The invention relates to a method for method for formation of expanded austenite and/or expanded martensite by solution hardening of a cold deformed workpiece of a passive alloy, which method comprises a first step of dissolving at least nitrogen in the workpiece at a temperature T 1 , which is higher than the solubility temperature for carbide and/or nitride and lower than the melting point of the passive alloy, and a subsequent second step of dissolving nitrogen and/or carbon in the work piece at a temperature T 2 , which is lower than the temperature at which carbides and/or nitrides form in the passive alloy. The invention further relates to a member, such as a lock washer for securing bolts or nuts prepared using the method.

TECHNICAL FIELD

The invention relates to a method for formation of expanded austeniteand/or expanded martensite by solution hardening of a cold deformedworkpiece of a passive alloy. The method provides a hardened alloy inwhich substantially no carbides and/or nitrides are formed. The methodalso provides a corrosion resistant surface while retaining the corestrength of the material obtained from the cold deformation. Theinvention further relates to a member solution hardened by the method.Such members are particularly relevant in the fields of medico, food,automotive, chemical, petrochemical, pharmaceutical, marine, package,watches, cutlery/tableware, medical, energy, pulp & paper, mining, orwaste water technology.

BACKGROUND

Stainless steel and other passive alloys are typically materials withgood corrosion resistance, but with relatively poor tribologicalcharacteristics, e.g. adhesive wear characteristics. To solve thisproblem stainless steel and comparable alloys can be surface hardened atlow temperature (below 450-550° C.) by dissolution of nitrogen and/orcarbon, by which is obtained a zone of so-called expanded austenite oralternatively expanded martensite. This zone is a supersaturatedsolution of carbon and/or nitrogen in austenite or martensite and ismetastable with respect to carbide/nitride formation. Such lowtemperature processes can be based on gas, plasma or molten salt; gasprocesses require use of special activation techniques, whereas forplasma and salt bath activation is immediately achieved and no specialtreatment is necessary. Thereby a surface zone is obtained in thematerial, which surface zone contains large amounts of nitrogen and/orcarbon; this is due to the relatively low process temperature. Thematerial thereby becomes surface hardened and retains its corrosionresistance. Most passive alloys, such as stainless steel, however cannotimmediately be solution hardened with nitrogen and/or carbon, sincethese passive alloys have an impermeable oxide layer, also called thepassive layer, which is the reason for the good corrosioncharacteristics, but which prevents solution of e.g. nitrogen andcarbon. Special techniques for removal of this passive layer aretherefore required. These techniques are known to the skilled person.

Most employed technological components are used in a machined condition,which means that the material is inhomogeneously cold deformed(plastically deformed). In many applications such cold deformation isdesirable from a component-strength-consideration; the component wouldnot work if it did not have the strength increase from the workhardening induced by cold deformation. This creates a big problem ifsuch cold machined components are surface hardened in a low temperatureprocess, so that the surface is changed to expanded austenite ormartensite under uptake of nitrogen and/or carbon. The presence ofplastic deformation (defects in the microstructure) in the materialimplies that nitrides and carbides develop easier by reaction ofnitrogen and carbon with e.g. chromium (Cr), which is an alloyingelement in stainless steel. Consequently an amount of Cr is removed fromsolid solution and bound as chromium nitride/chromium carbide. Thisimplies that the corrosion characteristics are deteriorated because lesschromium is available for maintenance of the passive layer. In localareas such Cr-depletion can be pronounced and result in loss ofcorrosion protection at the surface of the area. The precipitation ofnitrides/carbides is called sensitisation. In particular on dissolutionof nitrogen this phenomenon is very pronounced, because chromiumnitrides are more stable than chromium carbides and can be formed atlower temperature. This means that the temperature at thelow-temperature process must be lowered (further) to avoidsensitisation, which is undesirable since the process thereby proceedsmore slowly. For extreme degrees of deformation in stainless steel thereis perhaps not even a lower limit to sensitisation.

At low-temperature hardening of cold deformed stainless steel workpiecessensitisation will occur in connection with the low-temperaturedissolution of nitrogen and/or carbon, which takes place at temperaturesbelow 550° C. To solve the problem with sensitisation in cold deformedmaterials upon low-temperature surface hardening a full annealing of thecomponents has—where possible—been made by a so-called austenitisationin vacuum or hydrogen atmosphere. Full annealing is a process, which iscarried out at temperatures above 1020° C., typically in the range1020-1120° C. Thereby the cold deformation in the material isannihilated and the low-temperature dissolution can be carried outwithout the risk of sensitisation. However, the process provides theproblem that the strength of the cold-worked metal is reduced—this isreferred to as a so-called egg shell effect in the material, i.e. thematerial becomes soft with a hard thin surface, when the workpiece issubsequently low-temperature hardened. By carrying out anaustenitisation the core strength of the material is reduced to that ofannealed material, and this process requires that the core strength ofthe treated component is a design parameter of less importance.

Another possibility is to employ a carburising process where only carbonis dissolved in the material at low temperature, i.e. formation ofcarbon expanded austenite. Sensitisation is not as critical for carbondissolution as it is for nitrogen dissolution (nitriding andnitrocarburising) and hence leads to less influence on the corrosionresistance. However, for components with a strong degree of colddeformation even this is considered detrimental. Another disadvantage byonly employing carbon dissolution is that a lower surface hardness isobtained than for nitrogen dissolution and that the composition profile(hardness) cannot be adjusted in the same way (see e.g. EP 1095170 B1and WO 2006/136166 A1).

In e.g. Georgiev et al, Journal of Materials Science and Technology,Vol. 4, 1996, No. 4, pp. 28 and Bashchenko et al, Izvestiya AkademiiNauk SSSR. Metally, no 4, 1985, pp. 173-178, it is shown that nitrogenand/or carbon can be dissolved in stainless steel at high temperature(above about 1050° C.) under equilibrium conditions. It is shown that byemploying high temperatures the problem with permeation of the passivelayer of stainless steel can be bypassed, since this becomes unstable atthese high temperatures. It is also described that the solubilitytemperature for chromium carbide and chromium nitride lies below thistemperature. Consequently, carbides and/or nitrides are not formed atthese high temperatures. The solubility of nitrogen/carbon is howeverrelatively limited and for austenitic stainless steels no actual surfacehardening occurs; this applies in particular for carbon. To avoidprecipitation of carbides/nitrides during cooling a fast cooling rate isrequired. For martensitic stainless steel types a significant hardeningof the surface can take place by fast cooling; however, the hardeningeffect is at a significantly lower level than obtained by processes forformation of expanded austenite.

WO 2008/124239 suggests a hybrid carburisation process with intermediaterapid quench, according to which a carbon hardened surface in a metalworkpiece can be formed without forming carbide precipitates bysubjecting the workpiece to both high temperature carburisation and lowtemperature carburisation, wherein immediately after high-temperaturecarburisation, the workpiece is rapidly quenched to a temperature belowwhich carbide precipitates form. The rapid quenching may be accomplishedusing e.g. immersion of the workpiece in water, oil or other coolingmedium such as a gas or molten salt. WO 2008/124239 fails to recognizethe issues of cold-deformation and formation of carbides and/or nitridesduring a subsequent low-temperature hardening.

There is a need for a method which allows low temperature dissolution ofnitrogen and/or carbon for hardening of passive alloys such as stainlesssteel, where the problems with sensitisation and/or adjusting thecomposition profile are solved.

To overcome the problem with sensitisation in connection with lowtemperature nitriding and/or carburising of cold deformed workpieces theprior art suggests to anneal the material first, so that partial or fullre-crystallisation is obtained; alternatively only a recovery of thematerial. Thereby the cold deformation in the material, and thestrengthening obtained from the cold deformation, is annihilated, but onthe other hand the low temperature dissolution can be carried outwithout problems with sensitisation. However, this solution fails toprovide components having high core strength.

The aim of the present invention is to provide a method, which allowsthe formation of expanded austenite or expanded martensite by lowtemperature nitriding and/or carburising of products shaped through colddeformation and prepared from passive alloys, in particular stainlesssteel, without sensitisation occurring in the workpiece and where thestrengthening effect obtained is comparable to or possibly even largerthan the strengthening effect obtained by cold deformation.

DESCRIPTION OF THE INVENTION

The present invention relates to a method for formation of expandedaustenite and/or expanded martensite by solution hardening of a colddeformed workpiece of a passive alloy, which method comprises a firststep of dissolving at least nitrogen in the workpiece at a temperatureT1, which is higher than the solubility temperature for carbide and/ornitride and lower than the melting point of the passive alloy, and asubsequent second step of dissolving nitrogen and/or carbon in theworkpiece at a temperature T2, which is lower than the temperature atwhich carbides and/or nitrides form in the passive alloy.

The first step of dissolving nitrogen in the workpiece at a temperaturehigher than the solubility temperature for nitride significantlyimproves the core strength of the passive alloy, such as stainlesssteel, in comparison to only re-crystallisation annealing of thematerial prior to low temperature hardening. The high temperaturedissolution of nitrogen is done at temperatures above the austenisationtemperature of the alloy, e.g. at least or above 1050° C. and below themelting point of the alloy. The strengthening effect of thishigh-temperature nitriding is, surprisingly, sufficient to compensatefor the loss of strength caused by annihilating the cold deformationwhile the workpiece is kept at the high temperature during nitriding.Furthermore, the high-temperature nitriding allows that low temperaturehardening can be performed at higher temperatures than usual withoutcreating problems with formation of nitrides and/or carbides, and thatit is easier to activate the passive surface on the material at thesubsequent low temperature surface hardening process. Thus, theformation of the hardened zone is accelerated. Furthermore, bettercorrosion characteristics are obtained, since nitrogen exists in solidsolution.

A significant improvement of the hardening of passive alloys can beobtained by the high temperature dissolution of nitrogen followed by lowtemperature nitriding, carburising or nitrocarburising. Any passivealloy in which expanded austenite or expanded martensite may form isrelevant to the invention, and stainless steel is preferred, inparticular cold deformed austenitic stainless steel.

The subsequent low temperature dissolution of nitrogen and/or carbon,which takes place at temperatures below the temperature at whichcarbides and/or nitrides form in the passive alloy, such as below450-550° C. dependent on the process, may in the subsequent second stepbe carried out on a material, which does not contain plasticdeformation, but which has a strength on level with a plasticallydeformed workpiece. This means that the risk of sensitisation is reducedsignificantly. The presence of nitrogen and optionally carbon in solidsolution in stainless steel have even been found to give a faster lowtemperature process, than can be obtained using methods of the priorart, since the diffusion coefficients of nitrogen and carbon increasewith increasing carbon/nitrogen content. Thus, in certain examples thepassive alloy is a stainless steel containing nitrogen and/or carbon.

With the present invention it is possible to carry out a low temperaturehardening of passive materials, and in particular stainless steel, ofeven strongly cold deformed components without occurrence ofsensitisation of the material and without loss of strength. Colddeformed material treated with the method of the invention may evenobtain a significantly better corrosion resistance than untreatedmaterial. Conducted experiments have shown that the strength which isobtained by dissolution of nitrogen and optionally carbon in stainlesssteel at high temperature, typically above 1050° C., may give a (core)strength or substrate bearing capacity, which is sufficient tocompensate for the loss of strength which occurs when the colddeformation is removed by recrystallisation while heating to andmaintaining the high temperature during nitriding. That is, although thestrength obtained from cold deformation is lost, this loss iscompensated by the strength obtained from solution hardening withnitrogen and optionally carbon. Even relatively small amounts ofnitrogen give a significant increase of strength to provide the bearingcapacity, which is necessary for wear resistant expanded austenite.

The method of the present invention provides manufactured members havingat least the same strength as cold deformed members and at the same timebetter corrosion resistance, and further provides the advantage oftaking less time to perform.

Dissolution at temperature T1 and at temperature T2 may be performedusing any appropriate technology. For example dissolution at temperatureT1 and at temperature T2 may be performed in a gaseous process, e.g.using a gas containing nitrogen, such as ammonia, preferably N₂.Dissolution may also be performed using ion implantation, salt bath orplasma. It is preferred that dissolution at temperature T1 andtemperature T2 are carried out using gas, since this is a cheap andefficient solution and because all types of geometries may be treateduniformly, and there is a good temperature uniformity. Moreover, the useof a gas process means that the process is within the framework of thelaws of thermodynamics, which means that there are very well controlledprocessing conditions. It is further an advantage to employ gas becauseit has surprisingly been found that the high temperature process of theinvention makes the surface easier to activate using gas in the lowtemperature process. It is thus easier to remove the impermeable oxidelayer (passive layer), which is found on passive materials after a hightemperature dissolution. It is assumed that this is attributable to thepresence of nitrogen and optionally carbon which is dissolved at hightemperature.

The low temperature process may be carried out immediately after thehigh temperature process, but this is not mandatory. It is also possibleto perform the two processes with an offset in time and place. If theprocesses are carried out immediately after each other, e.g. with acooling step between the first and the second dissolution step, it ispossible to avoid that a passivation of the surface occurs and henceactivation prior to the low temperature process is superfluous. Thus,the invention also relates to an example wherein dissolution attemperature T2 takes place immediately after cooling from temperature T1without the passivation/activation of the surface in-between theexecution of the high temperature process and the low temperatureprocess. This may be done in the same furnace. When using gas therelevant gases containing nitrogen and/or carbon for use in the lowtemperature process may be supplied immediately when the material iscooled to temperature T2. However, the cooling is advantageously doneusing argon without any nitrogen present during cooling. An advantage ofusing gaseous processing is that it is possible to use gases, which donot activate the surface at temperature T2 in the low temperatureprocess. Other advantages of this example are that the hardening processthereby can be made cheaper and quicker.

A further advantage of the method of the invention is that bettercorrosion characteristics are obtained, since nitrogen exists in solidsolution. Dissolution of carbon does not change the corrosioncharacteristics. The material may be considered to be anitrogen-containing alloy, if the component is fully saturated withnitrogen. This will often be the case for thin-walled workpieces, e.g.workpieces with a material thickness of up to 4 mm, such as a thicknessof 2-4 mm, which are treated with the method of the invention. Stainlesssteel workpieces which are treated with the method of the inventiontherefore have a far better corrosion resistance compared to workpieces,which solely are treated with the low temperature process (see theexamples). An aspect of the invention relates to a thin-walledcomponent, or workpiece, of a cold deformed metal or alloy treatedaccording to the method of the invention.

For thin-walled components the material may be fully saturated withnitrogen by the high temperature process. In thick material a surfacezone of up to several millimetres, e.g. up to about 5 mm, may beobtained where nitrogen is in solid solution. In both cases the bearingcapacity of the material will be increased and comparable to what may beobtained by cold deformation. In an example of the invention dissolutionof nitrogen at temperature T1 is performed to obtain a diffusion depthin the range of 50 μm to 5 mm, which allows that workpieces with athickness of up to about 10 mm are fully saturated with nitrogen so thatparticularly strong workpieces are obtained. In general, the methodprovides that a thickness of expanded austenite or expanded martensiteof at least 5 μm is obtained in the workpiece, and the hardness of theexpanded austenite zone or the expanded martensite zone is at least 1000HV, such as more than 1050 HV.

The method may further comprise the intermediate step of cooling theworkpiece after the dissolution step at temperature T1 to a temperaturewhich is lower than the temperature at which carbides and/or nitridesform in the passive alloy, and in a specific example of the inventiondissolution at temperature T2 takes place immediately after cooling fromdissolution at temperature T1 without the occurrence of a passivation ofthe surface. In a certain exampel cooling after the first dissolutionprocess at temperature T1 takes place especially quickly, e.g. in aperiod of no more than 60 second, in the temperature interval in whichthere is the largest tendency for sensitisation and formation ofprecipitations, such as nitrides and/or carbides, for the relevantalloy. For stainless steel it has been found that this in particulartakes place in the interval from 900 to 700° C. where the materialshould be cooled quickly. In one embodiment the workpiece is cooled from900 to 700° C. in less than 60 seconds. In a preferred embodiment theworkpiece is cooled from 900 to 700° C. in less than 30 seconds. Therebythe formation of carbides and/or nitrides is substantially avoided, andthis is an advantage since these can react with the alloying elements instainless steel, such as chromium. The depletion of alloying elementsfrom solid solution and binding of these as nitrides and/or carbides issuppressed and the corrosion resistance characteristics are maintained.

In a preferred example the first dissolution step is performed in a gas,such as a gas containing N₂, e.g. substantially pure N₂ without othergasses than unavoidable impurities, and the cooling step is preferablyalso performed in a gas, which may be the same gas as that used in thefirst dissolution step. However, it is preferred that the gas in thecooling step is an inert gas not containing nitrogen (an nitrogen-freeinert gas) with argon being particularly preferred. In the context ofthe invention an “inert gas” is a gas that does not contain anysubstantial amount of molecules which interact with elements of thealloy; any inert gas not containing nitrogen is contemplated in theinvention, or mixtures of gasses. When an inert gas is employed in thecooling step it has surprisingly been found that the workpiece treatedin the method of the invention has a corrosion resistance, which is evensuperior to the corrosion resistance obtained using other cooling gases,or when the cooling step is performed using other methods. Inparticular, gasses containing nitrogen are believed to accelerateformation of nitrides when the cooling is performed in a gas containingnitrogen compared to cooling in an inert gas, so that a more robust andflexible method is provided with a cooling step using an inert gas.Cooling in an nitrogen-free inert gas may also allow longer coolingtimes than 60 s, but preferably cooling is performed an nitrogen-freeinert gas in less than 30 s, such as in less than 10 s.

The present inventors have further found that the advantageous effect ofusing an inert gas not containing nitrogen on the corrosion resistanceof a workpiece may also be obtained without subjecting the workpiece tothe second dissolution step. Thus, in a further aspect the inventionrelates to a method for solution hardening of a cold deformed workpieceof a passive alloy, which method comprises the steps of:

dissolving at least nitrogen in the workpiece at a temperature T1, whichis higher than the austenisation temperature and lower than the meltingpoint of the passive alloy,

cooling the workpiece after the dissolution step to a temperature whichis lower than the temperature at which carbides and/or nitrides form inthe passive alloy, wherein the cooling step takes place in an inert gasnot containing nitrogen.

The method according to this aspect may be combined freely with featuresrelating to the method according to the first aspect, and all suchcombinations are contemplated in the present invention. For example, allfeatures and variations discussed for the first dissolution step attemperature T1 are relevant in the method according to this secondaspect. Likewise, the method of the second aspect may also include asubsequent step of dissolving nitrogen and/or carbon in the workpiece ata temperature T2, which is lower than the temperature at which carbidesand/or nitrides form in the passive alloy.

In another aspect the invention relates to a member solution hardened bythe method of the first aspect or the above-mentioned further aspect.Any workpiece may be treated in the method, although it is preferredthat the workpiece has a thickness of up to about 10 mm, since this willprovide that the resulting member is fully saturated with nitrogen.Members which are solution hardened according to a method of the firstaspect or the further aspect may be used in any technological field.Fields of particular relevance comprise members for use in the technicalareas of medico, food, automotive, chemical, petrochemical,pharmaceutical, marine, package, watches, cutlery/tableware, medical,energy, pulp & paper, mining or waste water technologies. Members ofparticular interest comprise valves (butterfly valves, ball valves,control valves), steering bolts, nuts, washers, fasteners, nozzles,pumps, machinery components, semiconductor ASML, ferrule parts, ballbearings and bearing gages, pneumatic parts, membranes etc.

In a further aspect the invention relates to a member solution hardenedby the method according to the first aspect or the further aspect, wherethe member is a valve part or a part used in a valve.

In a further aspect the invention relates to a member solution hardenedby the method according to the first aspect or the further aspect, wherethe member forms an outer surface area of a design object, such as aclips for holding paper or notes, a sign plate, a holder, a lid of abox, cutlery, a watch, or a plate mounted together with a handle or aplate forming part of a lamp.

In a further aspect the invention relates to a member solution hardenedby the method according to the first aspect or the further aspect, wherethe member is part of a bearing, such as a part of a ball bearing, apart of a roller bearing, or a bearing cage.

In a further aspect the invention relates to a member solution hardenedby the method according to the first aspect or the further aspect, wherethe member is part of medical equipment, or medical instruments, ordental equipment, or dental instruments, or is a medical instrument or adental instrument.

In a further aspect the invention relates to a member solution hardenedby the method according to the first aspect or the further aspect, wherethe member is part of pharmaceutical equipment, such as a plate, anozzle, a shim, a pipe, or a grid.

In a further aspect the invention relates to a member solution hardenedby the method according to the first aspect or the further aspect, wherethe member is part of a car, such as a plate, a part in the exhaustsystem, a filter part, an engine part, a fixture, a handle, or a parthaving a decorative surface.

FIGURES OF THE DRAWINGS

FIG. 1 shows an isothermal transformation diagram (TTT diagram) for anitrogen-containing austenitic stainless steel.

FIG. 2 a shows a set of lock washers.

FIG. 2 b shows a set of lock washers with a bolt and nut.

FIG. 3 shows photomicrographs of a lock washer treated in a prior artmethod (left) and a lock washer treated by the method of the invention(right).

FIG. 4 shows photomicrographs of a lock washer treated in a prior artmethod (left) and a lock washer treated by the method of the invention(right).

FIG. 5 shows photomicrographs of a sample of AISI 316 treated in a priorart method (left) and by the method of the invention (right).

FIG. 6 shows photomicrographs of a sample of AISI 304 treated in a priorart method (left) and in the method of the invention (right).

FIG. 7 shows hardness profiles of stainless steel treated in a prior artmethod and by the method of the invention.

FIG. 8 shows lock washers treated in two different embodiments of themethod of the invention.

FIG. 9 shows photomicrographs of samples of AISI 316 treated in a priorart method (right) and by the method of the invention (left).

DEFINITIONS

In the context of the present invention the terms “expanded austenite”and “expanded martensite” describe an austenite or martensite,respectively, which has been supersaturated with nitrogen or carbon, ornitrogen and carbon (with respect to nitride or carbide formation).Expanded austenite and expanded martensite may be specified asnitrogen-expanded or carbonexpanded, or the expansion may be specifiedas nitrogen- and carbonexpanded. However, in the context of theinvention “expanded austenite” and “expanded martensite” generally referbroadly to austenite or martensite, respectively, expanded withnitrogen, carbon or any combination of nitrogen and carbon. A review ofexpanded austenite is provided by T. L. Christiansen and M. A. J. Somers(2009, Int. J. Mat. Res., 100: 1361-1377), the contents of which arehereby included by reference. Any alloy in which “expanded austenite” or“expanded martensite” may be formed is contemplated for the method ofthe invention. Expanded austenite or expanded martensite may form in thesurface of an alloy when the alloy is subjected to solution of nitrogenor carbon, or nitrogen and carbon, and the expanded austenite orexpanded martensite may also be referred to as a “zone” of expandedaustenite or expanded martensite. In the context of the presentinvention the term “zone” should be understood in relation to thethickness of the treated material so that “zone” is comparable to thethickness of expanded austenite or expanded martensite. The method ofthe invention provides that a thickness of expanded austenite orexpanded martensite of at least 5 μm is obtained in the workpiece; thethickness of the expanded austenite or expanded martensite may be up toabout 50 μm or higher.

In terms of the invention an “alloying element” may refer to a metalliccomponent or element in the alloy, or any constituent in the analysis ofthe alloy. In particular, alloys of relevance in the method of theinvention comprise an element that may form nitrides and/or carbideswith present nitrogen and carbon, respectively. The method of theinvention advantageously provides a surface free from nitrides andcarbides of alloying elements. It is however also contemplated in theinvention that an alloy may comprise only a single metallic elementcapable of forming nitrides and/or carbides. An alloy may also compriseother elements, such as semi-metallic elements, inter-metallic elements,or non-metallic elements. Alloying elements capable of forming nitridesand/or carbides may typically be metallic elements providing corrosionresistance to the alloy due to formation of a passive oxide layer withthe alloying element. The terms “nitride” and “carbide” as used in thecontext of the invention refer to nitrides and carbides formed betweenalloying elements and nitrogen and carbon, respectively. An exemplarynitride is chromium nitride, CrN or Cr₂N although terms “nitride” and“carbide” are not limited to nitrides and carbides with chromium.

By the term “passive” in connection with alloys or metals is to beunderstood an alloy, which has an oxide layer on the surface. The alloycan be both self-passivating or be passivated as a consequence of aprocess to which the alloy is subjected. Belonging to the group ofself-passivating alloys are those, which have a strong affinity tooxygen (e.g. Cr, Ti, V), including alloys containing such alloyingelements (e.g. stainless steel which essentially is an Febased alloycontaining at least 10.5% Cr).

By the term “cold deformation” (also named “cold working”) is to beunderstood a plastic deformation induced in the material by externalforces at a temperature below the recrystallization temperature of thematerial. Cold deformation may be provided by an actual plastic shapechange, such as forging, extrusion, shaping, drawing, pressing, orrolling, and may also be caused by machining such as turning, milling,punching, grinding or polishing etc, or by a combination of theseprocesses.

By the term “sensitisation” is to be understood that nitrogen or carbonhave formed nitrides and carbides, respectively, by reaction with one ormore alloying elements otherwise utilized to form the protective oxidelayer on the surface, as for example chromium in stainless steel. Whensensitisation occurs, the free content of the alloying element, such aschromium, in solid solution is lowered to a level, which is no longersufficient to maintain a complete protective oxide layer, which meansthat the corrosion characteristics are deteriorated.

By the term “solubility temperature for carbide and/or nitride” is to beunderstood the temperature at which nitrides/carbides are not stable,and where already formed nitrides/carbides are dissolved. In general,alloys comprising metallic alloying elements capable of forming nitridesand/or carbides will have a temperature interval in which nitridesand/or carbides may form when nitrogen and carbon, respectively, arepresent. Thus, above this temperature interval, nitrides and carbideswill not form, and already formed nitrides/carbides are dissolved. Whennitrides or carbides exist, i.e. sensitisation has occurred, thesecarbides can generally only be removed by exposing the sensitised metalto a temperature above the austenisation temperature. Furthermore, suchalloys have a temperature below the temperature interval, where nitridesand carbides will not form, although nitrides or carbides already formedin an alloy cannot be removed at the low temperature.

The “austenisation temperature” is typically the temperature used whenheat treating an alloy in order to dissolve carbides, and “austenisationtemperature” may thus correspond to the “solubility temperature forcarbide”. At the austenisation temperature the alloy is in theaustenitic phase. The temperature at which a steel alloy changes phasefrom ferrite to austenite is typically at a somewhat lower temperaturethan the austenisation temperature.

The austenitsation temperature as well as the temperature at whichcarbides and/or nitrides form in a passive alloy are generallywell-known to the skilled person. Likewise is the temperature belowwhich nitrides or carbides will not form generally known to the skilledperson. Furthermore is the melting temperature of the alloy generallyknown to the skilled person. The temperatures may depend on thecomposition of the passive alloy, and for any given composition thesetemperatures are furthermore easily determined experimentally by theskilled person.

The alloying contents mentioned are expressed in percent by weight. Withrespect to compositions of alloys or of gas unavoidable impurities maynaturally also be present, even if this is not specifically mentioned.

Further Description of the Invention

FIG. 1 shows an example of an isothermal transformation diagram (TTTdiagram) for a nitrogen-containing austenitic stainless steel; thestainless steel has the composition Fe-19Cr-5Mn-5Ni-3Mo-0.024C-0.69N(from J. W. Simmons, PhD thesis, Oregon Graduate Institute of Scienceand Technology 1993). In FIG. 1 the temperature interval in whichnitrides may begin to form is indicated with “Cr₂N”. In the method ofthe invention the first step of dissolving nitrogen in the passive alloyis thus performed at a temperature T1 above the austenisationtemperature and the second step of dissolving nitrogen and/or carbon isperformed at a temperature T2 below the temperature interval wherenitrides and/or carbides can form. Thus, temperature T1 is higher thantemperature T2. It is preferred that the workpiece is cooled, e.g.within a time span of 60 seconds, after the first dissolution step attemperature T1 to a temperature which is lower than the temperature atwhich carbides and/or nitrides form in the passive alloy. The passivealloy of the workpiece will thus be stabilised with respect to formationof nitrides and/or carbides, and the second dissolution step may then beperformed as desired. The austenisation temperature may also be referredto as “high” temperature in the context of the invention. Likewise, thetemperature below the temperature at which carbides and/or nitrides formis also referred to as “low” temperature.

The method of the invention comprises steps of dissolving nitrogenand/or carbon in the passive alloy. The step of dissolving nitrogen mayalso be referred to as the “dissolution of nitrogen” or “nitriding”, andlikewise step of dissolving carbon may also be referred to as the“dissolution of carbon” or “carburising”. When both nitrogen and carbonare dissolved in the same process step may be referred to as“nitrocarburising”.

In a certain aspect the invention relates to a member solution hardenedby the method of the invention. In the contexts of the invention“treated” should be understood broadly. In particular, the term“treated” means that method of the invention has been employed in themanufacture of the member. Thus, the invention also relates to a membermanufactured using the method of the invention and the terms “treatedin” and “manufactured using” may be used interchangeably. The method ofthe invention may be the last step in the manufacture of the member or amember treated by the method may also be subjected to further processingsteps to provide the final member.

In the context of the present invention a “thin-walled component” is acomponent of a size allowing the component to be fully saturated withnitrogen and/or carbon in the method of the invention. Thus, a“thin-walled component” may have a material thickness, e.g. in itssmallest dimension, of up to, and including, about 10 mm, such as athickness of about 2 mm to about 4 mm or a thickness in the range from0.2 mm to 8 mm, or a thickness in the range from 0.4 mm to 6 mm, or athickness in the range from 0.5 mm to 5 mm, or a thickness in the rangefrom 1.5 mm to 4.5 mm. The method may be used with any thin-walledcomponent.

The novel and unique way in which one or more of the above aims isobtained, is by the provision of a method for formation of expandedaustenite and/or expanded martensite by solution hardening of a colddeformed workpiece of a passive alloy, which method comprises a firststep of dissolving at least nitrogen in the workpiece at a temperatureT1, which is higher than the solubility temperature for carbide and/ornitride and lower than the melting point of the passive alloy, and asubsequent second step of dissolving nitrogen and/or carbon in theworkpiece at a temperature T2, which is lower than the temperature atwhich carbides and/or nitrides form in the passive alloy.

The invention is especially suitable for stainless steels and comparablealloys, where expanded austenite or martensite can be obtained in a lowtemperature dissolution process. In general, alloys based on iron,nickel and/or cobalt comprising chromium are relevant for the method.The chromium content may vary and may as an example be up to about 10%.In other examples the chromum content may be at about 10% or at least10%. Thus, the invention in one example relates to a method for solutionhardening of a cold deformed workpiece of stainless steel. Nitrogen andoptionally also carbon can be dissolved in the stainless steel at atemperature, which is higher than the austenisation temperature of thestainless steel, e.g. the solubility temperature for carbide and/ornitride for present alloying elements, such as chromium. Even relativelysmall amounts of nitrogen give a significant increase in strength toprovide a load bearing capacity, which is necessary for wear resistantexpanded austenite. In an example of the invention the hardness of theexpanded austenite zone or the expanded martensite zone is at least 1000HV.

In an example of the invention the stainless steel is an austeniticsteel. This material is relatively soft compared to e.g. martensiticstainless steel. Therefore, it is especially advantageous for thismaterial that nitrogen and optionally carbon is dissolved at the hightemperature process. Thereby, it is obtained that the austenitic steelreceives a sufficient core strength to compensate for the loss ofstrength, which takes place when the cold deformation is annihilated andthat it is then possible to dissolve nitrogen and/or carbon at lowtemperature without problems with precipitation, such as nitrides and/orcarbides. In further examples of the invention the passive alloy isselected from the group comprising stainless steel, austenitic stainlesssteel, martensitic stainless steel, ferritic stainless steel,precipitation hardenable (PH) stainless steel or ferritic-austeniticstainless steel; a ferritic-austenitic stainless steel may also bereferred to as a duplex stainless steel.

The content of nitrogen and optionally carbon, which is dissolved at thehigh temperature process in stainless steel will typically be less than1% by weight, but may, if desired, be higher. This may e.g. be obtainedby applying a higher nitrogen and optionally carbon activity, forexample in the form of a higher partial pressure of N₂ in a gaseousprocess. The content of nitrogen and/or carbon, which is obtained instainless steel at the low temperature dissolution may be as high as 14%by weight and 6% by weight, respectively.

In a preferred example the above dissolution of nitrogen and/or carbontakes place at the temperature T1 using gas, which contains nitrogen andoptionally carbon, but it may also be performed by ion implantation,plasma assistance or by salt bath. In a preferred example a nitrogencontaining gas, such as N₂, is used. The pressure of the gas may be upto several bar, but it may also be below 1 bar, such as 0.1 bar. It isan advantage to employ gas, since all types of geometries may be treateduniformly and there is a good temperature uniformity.

In an example of the invention dissolutions are performed at temperatureT1 and temperature T2 using gas. The gas contains nitrogen and/orcarbon. In certain examples dissolution at temperature T2 is performedin a process selected from the group comprising a gas-based process, ionimplantation, salt bath or plasma.

In an example of the invention a diffusion depth of 50 μm to 5 mm isobtained by dissolution of nitrogen and optionally carbon at temperatureT1. This provides both a hard surface and a strengthening of the core ofthe material. Thereby a full hardening of thin-walled components with amaterial thickness comparable with, or up to about twice the dissolutiondepth, may be obtained since dissolution normally takes place from bothsides of the workpiece. For thicker components a relatively thicksurface zone where nitrogen and optionally carbon is in solid solutionis obtained. This provides support for the expanded austenitic layer,which is formed in the surface in the subsequent low temperatureprocess. For thin-walled workpieces a fullnitriding/carburising/nitrocarburising of the workpiece may thus beobtained. Even if this is not fully obtained the dissolution will be asignificant advantage, especially for thin-walled workpieces, wherestrict requirements to the corrosion resistance, and to the bearingcapacity, are relevant, since these are improved significantly in themethod of the invention.

In an example of the invention the temperature T1 is above 1000° C.,such as at least 1050° C., or it may be at least 1100° C., such as 1120°C. or 1160° C., at least 1200° C., or at least 1250° C. The upper limitfor the temperature is below the melting point of the treated materials.For stainless steel the melting point is about 1600° C. In an example ofthe invention temperature T1 is below 1600° C., such as below 1500° C.,or below 1400° C., such as below 1350° C. In an example of the inventiontemperature T1 is in the range of 1050 and 1300° C., such as at about1150° C. It is important that the temperature is higher than thesolubility temperature for the relevant carbides and/or nitrides, whichmay potentially be formed in the material, but however below the meltingpoint of the treated material. When gas is employed in dissolution attemperature T1 the employed temperature may be chosen with considerationto the gas mixture and the applied gas pressure.

In another example of the invention carbon is dissolved at temperatureT2, and temperature T2 is below 550° C., preferably the range of300-530° C. during carburising.

In yet another example of the invention nitrogen is dissolved attemperature T2, and temperature T2 is below 500° C., such as below 470°C., preferably the range of 300-470° C. during nitriding.

In yet another example of the invention nitrogen and carbon aredissolved at temperature T2, and temperature T2 is below 500° C., suchas below 470° C., preferably the range of between 300-470° C. duringnitrocarburising.

In an example of the invention the high temperature dissolution iscarried out at temperature T1 for at least 20 min, such as for at least30 minutes, or for at least 1 hour, or for at least 1.5 hours, or for atleast 2 hours or for at least 3 hours, or for at least 4 hours, or forat least 5 hours, or for at least 10 hours or for at least 15 hours. Inprinciple there is no upper time limit, since no nitrides or carbidesare formed at temperature T1. At extended treatment the material may,depending on its thickness, be saturated with nitrogen and optionallycarbon, i.e. be fully nitrided or nitrocarburised.

In an example of the invention the method comprises the intermediatestep of cooling the workpiece after the dissolution step at temperatureT1 to a temperature which is lower than the temperature at whichcarbides and/or nitrides form in the passive alloy, for example thematerial may be cooled to ambient temperature after the dissolution attemperature T1. It is particularly preferred that the second dissolutionstep at temperature T2 is performed immediately after the cooling step;this will avoid passivation of the workpiece, i.e. formation of an oxidelayer. In an example of the invention the cooling takes place in thesame gas as the dissolution, e.g. gas cooling with N₂ under highpressure, such as the range of 6 and 10 bar, such as at 7 bar or at 8bar, or at 9 bar. It is preferred that the cooling takes place in aninert gas not containing nitrogen, such as a noble gas, e.g. helium(He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), or radon (Rn), orany mixture of these, with argon being particularly preferred. Inanother example cooling takes place in argon at high pressure, e.g. therange of 4 and 20 bar, such as in the range of 6 and 10 bar, such as at7 bar or at 8 bar, or at 9 bar.

The invention further relates to a lock washer (see FIGS. 2 a and 2 b)of stainless steel for securing bolts and nuts, which is dissolutionhardened using the method of the invention. The lock washer isrelatively thin-walled, so that by hardening the lock washer using themethod of the invention a significant and necessary improvement of bothstrength and corrosion resistance of the lock washer is obtained. In anembodiment of the invention the lock washer has a first side with radialteeth and an opposite other side, the camside, with cams. The lockwashers are used in pairs mounted with the cams against each other toobtain a key lock effect. They are especially suitable to effectivelylock bolt assemblies which are exposed to extreme vibrations or dynamicloads and to corrosive environment, such as salt water. There aretherefore strong requirements to the strength and corrosion resistanceof these washers.

The invention is especially suitable for stainless steels and comparablealloys, in which expanded austenite or martensite can be obtained at alow temperature dissolution process. The invention is, however, genericin nature: a high temperature dissolution process with nitrogen andoptionally carbon in passive alloys, such as iron-based alloys,cobalt-based alloys, nickel-based alloys or chromium-based alloys, whichprovides strength and an improved low temperature dissolution processwith respect to corrosion, processing rate and strength.

The following examples with accompanying figures explain examples of theinvention in further detail.

Example 1

Hardening of Key Lock Washers of Cold Deformed Austenitic StainlessSteel, AISI 316, by a Method of the Prior Art and a Method of theInvention.

Two identical key lock washers of cold deformed austenitic stainlesssteel AISI 316L were hardened. FIG. 2 shows a key lock washer set 1 ofsaid key lock washers 2 and illustrates the use of these. Each washer 2has a first side 3 with radial teeth 4 and an opposite other camside 5with cams 6. During use of the key lock washer set 1 the washers 2 areplaced as shown with the camsides 5 facing each other. The two key lockwashers were solution hardened with nitrogen and carbon at a temperatureof 440° C. One washer was hardened by a method of the invention, i.e. ina high temperature process and subsequently in a low temperatureprocess, and the other washer was directly surface hardened with thesame low temperature process, i.e. of the prior art. The washers wereanalysed with optical microscopy. FIG. 3 and FIG. 4 in the left panelshow the washer, which was only surface hardened with a nitrocarburisingprocess conducted using a gas containing nitrogen and carbon at atemperature of 440° C. for 16 hours at atmospheric pressure. The outersurface in the nitrogen containing zone appears partly sensitised(chromium nitride precipitations). The deformed substrate appearsstrongly deformed and becomes clearly influenced by the employed etchingliquid to development of the micro structure. FIG. 4 shows an enlargedversion of FIG. 3.

FIG. 3 and FIG. 4 in the right panel show the washer treated by themethod of the invention. The washer was exposed to a nitrogen containingatmosphere (N₂ gas) at a temperature above 1050° C. and was subsequentlyquickly cooled in the same gas. Thereby the material was austenitisedcompletely and the material was fully saturated with nitrogen. Then thewasher was surface hardened with a nitrocarburising process conductedusing a gas containing nitrogen and carbon at a temperature of 440° C.for 16 hours at atmospheric pressure, whereby expanded austenite wasformed in the surface in a zone with a thickness of at least 5 μm. Thenitrocarburised nitrogen-containing zone was not sensitised and thesubstrate was clearly without cold deformation. The substrate hardness(260-300 HV0.5) and the surface hardness (1200-1400 HV0.005) in the twowashers are however practically identical. The corrosion resistance(exposure time in salt spray chamber (ISO 9227)) of the washer, wherethe method of the invention was employed, is many times better than forthe washer which was only surface hardened (time in the chamber untilcorrosion was observed). The washer which was treated with the method ofthe invention did not exhibit corrosion after 400 hours whereas thewasher which was directly low temperature hardened did exhibit clearlyvisible corrosion already after 20 hours.

Example 2

Hardening of Cold Deformed Austenitic Stainless Steel, AISI 316, by aMethod of the Prior Art and a Method of the Invention.

Two identical components (back ferrules) of cold deformed austeniticstainless steel AISI 316 were solution hardened with nitrogen and carbonat a temperature of 440° C. One component was hardened by a method ofthe invention, i.e. in a high temperature process and subsequently in alow temperature process and the other component was directly surfacehardened with the same low temperature process. FIG. 5 in the left panelshows the microstructure analysed with optical microscopy of acomponent, which was only surface hardened with a nitrocarburisingprocess conducted using a gas containing nitrogen and carbon at atemperature 440° C. for 12 hours. The outer surface in the nitrogencontaining zone appears partly sensitised with clear precipitations ofCrN in the outermost surface. FIG. 5 in the right panel shows acomponent treated with the method of the invention. The component wasexposed to a nitrogen containing atmosphere (N₂ gas) at a temperatureabove 1050° C. and was subsequently quickly cooled in the same gas. Thenthe component surface was hardened with a nitrocarburising process in alow temperature process conducted using a gas containing nitrogen andcarbon at a temperature of 440° C. for 12 hours. The nitrocarburisednitrogen containing zone was not sensitised. The substrate hardness(260-300 HV0.5) and the surface hardness (1200-1400 HV0.005) in the twocomponents are, however, practically identical. The total layerthickness of the expanded austenite zone is in both cases approximately20 μm. The outermost layer is nitrogen expanded austenite, and theinnermost layer is carbon expanded austenite. The corrosion resistancefor both components was tested in a 14% by weight sodium hypochloritesolution. The component which was treated with the method of theinvention does not exhibit corrosion after 24 hours, whereas thecomponent, which was directly low-temperature hardened exhibits clearcorrosion after only 10 minutes. The component where the method of theinvention was employed thus differs in having a significantly bettercorrosion resistance than the workpiece, which was directlynitrocarburised.

Example 3

Hardening of Cold Deformed Austenitic Stainless Steel AISI 304 Plate bya Method of the Prior Art and a Method of the Invention.

Two identical components of cold rolled (deformed) austenitic stainlesssteel plate, AISI 304, were solution hardened with nitrogen and carbonat a temperature of 440° C. One component was hardened by a method ofthe invention, i.e. in a high temperature process and subsequently in alow temperature process and the other component was directly surfacehardened with the same low temperature process. FIG. 6 in the left panelshows a component, which was only surface hardened with anitrocarburising process conducted using a gas containing nitrogen andcarbon at a temperature of 440° C. for 20 hours and subsequentlycorrosion tested by exposure to 14% by weight sodium hypochloritesolution for 70 minutes. FIG. 6 in the right panel shows the componenthardened with the method of the invention. The component was exposed toa nitrogen containing atmosphere (N₂ gas) at a temperature of 1150° C.for 30 minutes and was subsequently cooled quickly in the same gas. Thenthe component was surface hardened with a nitrocarburising processconducted using a gas containing nitrogen and carbon at a temperature of440° C. for 20 hours. Finally the component was exposed to corrosiontest by exposure to 14% by weight sodium hypochlorite solution. Thesurface appears unaffected by the corrosion test even after 16 hours ofexposure. In the component which was directly low temperature hardenedclear corrosion attacks are seen after short term exposure/corrosiontest (70 minutes). The component where the method of the invention wasemployed thus differs in having a much better corrosion resistance.

Example 4

Hardness Profiles of Cold Deformed Stainless Steel Treated by a Methodof the Prior Art and a Method of the Invention.

Two identical components of cold deformed austenitic stainless steelwere treated in a method of the prior art and according to the method ofthe invention. The samples were exposed to a nitrogen containingatmosphere (N₂ gas) or to an atmosphere of hydrogen (H₂) at atemperature above 1050° C. and were subsequently cooled quickly in theargon (for the N₂-treated sample) or H₂ gas. The component surfaces werethen hardened by nitrocarburising in a low temperature process conductedusing a gas containing nitrogen and carbon at a temperature of 440° C.for 12 hours. The nitrocarburised zones were not sensitised. Thehardness profiles of the samples were analysed and the results are shownin FIG. 7. It is evident from FIG. 7 that the sample treated at hightemperature in the nitrogen containing atmosphere (“EXPANITE ON HTSN”)retained the core strength of the material whereas the core strength wasannihilated in the high temperature annealing in hydrogen (“EXPANITE ONANNEALED”).

Example 5

Argon Cooling Following High-Temperature Solution Hardening withNitrogen.

Lock washers of cold deformed austenitic stainless steel, AISI 316L, asdescribed in Example 1 and illustrated in FIG. 2 were exposed to anitrogen containing atmosphere (N₂ gas) at a temperature above 1050° C.before quickly cooling to ambient temperature in either the sameatmosphere or an atmosphere of argon. The samples were not subjected tofurther surface hardening. The corrosion resistance of the componentswas tested in a 14% by weight sodium hypochlorite solution. FIG. 8 showsthree exemplary lock washers cooled in argon (left side) and three lockwashers cooled in nitrogen (right side). The argon cooled lock washershad far superior corrosion resistance than lock washers cooled innitrogen, which showed clear signs of corrosion.

Example 6

Hardening of cold deformed austenitic stainless steel, AISI 316,component by a method of the prior art and a method of the invention.

The corrosion resistance of cold deformed austenitic stainless steelAISI 316 treated according to the invention was compared with a similarcomponent treated with a process of the prior art. The corrosion testingwas performed by submerging the two surface hardened components into 14%by weight sodium hypochlorite solution for 18 hours.

FIG. 9 in the left panel shows the component treated according to theinvention, i.e. in a high temperature process and subsequently in a lowtemperature process and the other component in the right panel wasdirectly surface hardened solely with a low temperature process.

The surface of the component treated according to the invention appearsunaffected by the corrosion test even after 18 hours of exposure. In thecomponent which was treated according to the prior art, corrosionattacks were observed after short term exposure (7 minutes). Thecomponent where the method of the invention was employed thus differs inhaving a much better corrosion resistance.

1-23. (canceled)
 24. A method for formation of expanded austenite and/orexpanded martensite by solution hardening of a cold deformed workpieceof a passive alloy based on iron, nickel and/or cobalt and comprising atleast 10% chromium or an iron based alloy containing at least 10.5%chromium, which method comprises a first step of dissolving at leastnitrogen in the workpiece at a temperature T1, which is higher than thesolubility temperature for carbide and/or nitride and lower than themelting point of the passive alloy, wherein dissolution of nitrogen attemperature T1 is performed to obtain a diffusion depth in the range of50 μm to 5 mm, and a subsequent second step of dissolving nitrogenand/or carbon in the workpiece at a temperature T2 of at least 300° C.,which temperature T2 is lower than the temperature at which carbidesand/or nitrides form in the passive alloy, the method further comprisingthe intermediate step of cooling the workpiece after the dissolutionstep at temperature T1 to a temperature which is lower than thetemperature at which carbides and/or nitrides form in the passive alloy.25. The method according to claim 24, wherein dissolution at temperatureT2 takes place immediately after cooling from dissolution at temperatureT1.
 26. The method according to any of the claim 24 or 25, wherein thecooling step takes place in an inert gas, preferably an inert gas notcontaining nitrogen.
 27. The method according to claim 26, wherein theinert gas apart from unavoidable impurities is argon.
 28. The methodaccording to any one of the claims 24 to 27, wherein nitrogen and carbonare dissolved at temperature T1.
 29. The method according to any one ofthe claims 24-28, wherein the passive alloy is selected from the groupcomprising stainless steel, austenitic stainless steel, martensiticstainless steel, ferritic stainless steel, precipitation hardenable (PH)stainless steel or ferritic-austenitic stainless steel.
 30. The methodaccording to any of the preceding claims, wherein dissolution attemperature T1 is performed using a gas containing nitrogen, preferablyN₂.
 31. The method according to any of the preceding claims, whereindissolution at temperature T2 is performed in a process selected fromthe group comprising a gas-based process, ion implantation, salt bath orplasma.
 32. The method according to any of the preceding claims, whereindissolutions at temperature T1 and temperature T2 are performed using agas.
 33. The method according to any of the preceding claims, whereintemperature T1 is at least 1050° C., such as in the range of 1050° C. to1300° C.
 34. The method according to any one of claims 30 to 33, whereinthe cooling after the dissolution at temperature T1 takes place in thesame gas which is used in the dissolution step at temperature T1. 35.The method according to any one of the preceding claims, wherein thecooling from the temperature 900° C. to 700° C. is performed in lessthan 60 seconds.
 36. The method according to any of the precedingclaims, wherein carbon is dissolved at temperature T2, and temperatureT2 is below 550° C., preferably in the range of 300-530° C.
 37. Themethod according to any of the preceding claims, wherein nitrogen isdissolved at temperature T2, and temperature T2 is below 500° C.,preferably in the range of 300-470° C.
 38. The method according to anyof the preceding claims, wherein nitrogen and carbon are dissolved attemperature T2, and temperature T2 is below 500° C., preferably in therange of 300-470° C.
 39. The method according to any of the precedingclaims, wherein a thickness of expanded austenite or expanded martensiteof at least 5 μm is obtained in the workpiece.
 40. The method accordingto any of the preceding claims, wherein the hardness of the expandedaustenite zone or the expanded martensite zone is at least 1000 HV. 41.The method according to any one of claims 25 to 40, wherein dissolutionat temperature T2 occurs in the same furnace as dissolution attemperature T1.
 42. The method according to any of the preceding claims,wherein the cold deformation in the cold deformed workpiece has beenprovided by an actual plastic shape change, such as forging, extrusion,shaping, drawing, pressing, or rolling, or by machining such as turning,milling, punching, grinding or polishing etc, or by a combination ofthese processes.
 43. The method according to any of the precedingclaims, wherein the workpiece has a thickness of up to about 10 mm. 44.The member solution hardened by the method according to any of claims 24to
 43. 45. The member according to claim 44, wherein the workpiece has athickness of up to about 10 mm.
 46. The member according to claim 44 or45, wherein the member is a lock washer of stainless steel for securinga fixing part, such as bolts and/or nuts.
 47. A member according toclaim 46, wherein the lock washer has a first side with radial teeth andan opposite other side with cams.